U.S. patent number 4,176,080 [Application Number 05/839,221] was granted by the patent office on 1979-11-27 for detergent compositions for effective oily soil removal.
This patent grant is currently assigned to The Procter & Gamble Company. Invention is credited to Sharon J. Mitchell, Rodney M. Wise.
United States Patent |
4,176,080 |
Wise , et al. |
November 27, 1979 |
Detergent compositions for effective oily soil removal
Abstract
Compositions and methods for removing oily soils from fabrics
involving treatment with specific mixtures of solvents and solvent
soluble emulsifiers in an aqueous washing medium followed by
treatment with specified surface active agents to remove retained
solvent from fabrics. The compositions herein can be employed
singly in aqueous washing media to remove oily materials from
fabrics or can be admixed with other materials suitable for use in
a laundry procedure.
Inventors: |
Wise; Rodney M. (Cincinnati,
OH), Mitchell; Sharon J. (Cincinnati, OH) |
Assignee: |
The Procter & Gamble
Company (Cincinnati, OH)
|
Family
ID: |
25279172 |
Appl.
No.: |
05/839,221 |
Filed: |
October 3, 1977 |
Current U.S.
Class: |
8/137; 134/40;
510/277; 510/338; 510/340; 510/341; 510/342; 510/348; 510/349;
510/352; 8/142 |
Current CPC
Class: |
C11D
3/43 (20130101); D06L 1/16 (20130101); C11D
11/0017 (20130101) |
Current International
Class: |
C11D
11/00 (20060101); C11D 3/43 (20060101); D06L
1/00 (20060101); D06L 1/16 (20060101); C11D
007/24 () |
Field of
Search: |
;252/162,170,172,104,111,114,118,122,139,153 ;134/40
;8/137,142 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Weinblatt; Mayer
Attorney, Agent or Firm: Gebhardt; Edmund F. O'Flaherty;
Thomas H. Witte; Richard C.
Claims
What is claimed is:
1. A cleaning product composition for removing oily soil from
fabrics in an aqueous washing medium consisting essentially of:
(1) a discrete unit of an oily soil dissolving agent consisting
essentially of:
(a) from about 20% to about 97% by weight of a water-insoluble
solvent selected from the group consisting of:
(i) alkanes and alkenes having a flash point not lower than about
65.degree. C. (Tag closed cup), an initial boiling point not lower
than about 130.degree. C., a solidification point not above about
20.degree. C. and a carbon chain length from about 10 to about 18;
and
(ii) fatty acid esters of the formula ##STR3## in which R.sub.1 is
an alkyl group with from about 7 to about 17 carbon atoms and
R.sub.2 is an alkyl group with from 1 to about 10 carbon atoms, the
sum of carbon atoms in R.sub.1 and R.sub.2 being from about 8 to
about 23;
(b) from about 3% to about 30% by weight of a water-in-oil
emulsifier soluble in said solvent, said emulsifier having an HLB
value of from about 2 to about 12 and consisting essentially of
from about 25% to 100% of emulsifier compounds with at least two
alkyl groups each having from about 9 to about 20 carbon atoms and
selected from the group consisting of:
(i) dialkyl sulfosuccinic acid and alkali metal, alkaline earth
metal, ammonium, and mono-, di-, and tri-C.sub.1-4 alkyl and
alkanol ammonium salts of dialkyl sulfosuccinic acid, said alkyl
groups each containing from about 9 to about 20 carbon atoms;
(ii) quaternary ammonium compounds with more than one long chain
alkyl group selected from the group consisting of di-C.sub.9-20
alkyl ammonium chloride, bromide, methyl sulfate, nitrate and
acetate and di-C.sub.9-20 alkyl imadazolinium quaternary ammonium
compounds;
(iii) alkyl or alkyl ethoxy diesters of phosphoric acid having the
formula ##STR4## in which both R.sub.1 and R.sub.2 are alkyl groups
containing from about 9 to about 20 carbon atoms, n and m are from
zero to about 8 and M is hydrogen or a salt forming cation, and
(iv) mixtures thereof;
(c) from 0% to about 77% water; and
(d) from 0% to about 77% detergency builders selected from the
group consisting of water soluble orthophosphates, polyphosphates,
phosphonates, carbonates, bicarbonates, polyhydroxysulfonates,
silicates, carboxylates and polycarboxylates, water-insoluble
aluminosilicates and mixtures thereof,
(2) a discrete unit or units of a solvent stripping agent
consisting essentially of from about 5% to 100% of a water-soluble
surfactant having an HLB value of from about 11 to about 18,
selected from the group consisting of anionic, nonionic,
zwitterionic, amphoteric and cationic surfactants and mixtures
thereof, from 0% to about 95% water and from 0% to about 95%
detergency builders selected from the group consisting of water
soluble orthophosphates, polyphosphates, phosphonates, carbonates,
bicarbonates, polyhydroxysulfonates, silicates, carboxylates and
polycarboxylates, water-insoluble aluminosilicates and mixtures
thereof, said discrete unit comprising from about 10% to about 80%
by weight of the total cleaning product.
2. The composition of claim 1 wherein said oily soil dissolving
agent consists essentially of from about 50% to about 95% of said
solvent and from about 5% to about 20% of said emulsifier.
3. The composition of claim 1 wherein said solvent stripping agent
is an aqueous solution consisting essentially of from about 10% to
about 50% of an anionic surfactant selected from the group
consisting of alkyl sulfates, alkyl benzene sulfonates, and alkyl
polyoxyether sulfates, said alkyl groups having from about 10 to
about 20 carbon atoms and said polyoxyether group having an average
of from about 2 to about 4 moles of ethylene oxide and from about
50% to about 90% water.
4. The composition of claim 1 wherein said solvent stripping agent
additionally consists essentially of from about 0.5% to about 15%
of a fabric sizing agent selected from the group consisting of
gelatinized starch and partially gelatinized starch and from 0% to
about 3% of a quaternary ammonium fabric softening and antistatic
agent selected from the group consisting of
(a) compounds having the formula ##STR5## wherein R.sub.1 is
hydrogen or an aliphatic group of from 1 to 22 carbon atoms;
R.sub.2 is an aliphatic group having from 12 to 22 carbon atoms;
R.sub.3 and R.sub.4 are each alkyl groups of from 1 to 3 carbon
atoms; and X is an anion selected from halogen, acetate, phosphate,
nitrate and methyl sulfate radicals;
(b) compounds having the formula ##STR6## wherein R.sub.6 is an
alkyl containing from 1 to 4, preferably from 1 to 2 carbon atoms,
R.sub.5 is an alkyl containing from 1 to 4 carbon atoms or a
hydrogen radical, R.sub.8 is an alkyl containing from 1 to 22,
preferably at least 15 carbon atoms, and X is an anion; and
(c) mixtures thereof.
5. The composition of claim 1 wherein said solvent is an alkane
with an average of from about 10 to about 16 carbon atoms.
6. The composition of claim 5 wherein said oily soil dissolving
agent consists essentially of from about 50% to about 95% of said
solvent and from about 5% to about 20% of said emulsifier.
7. The composition of claim 1 wherein said solvent stripping agent
is incorporated into said discrete unit of oily soil dissolving
agent but is restrained from intimate mixing with said oily soil
dissolving agent by a barrier material insoluble in said oily soil
dissolving agent selected from the group consisting of gelatin and
polyvinyl alcohol.
8. The composition of claim 7 wherein said discrete unit of oily
soil dissolving agent is from about 75 grams to about 1000 grams
and said solvent stripping agent is from about 50 grams to about
1000 grams.
9. A method of removing oily soil from fabrics consisting
essentially of:
(1) contacting said fabrics with an aqueous washing medium
consisting essentially of:
(a) from about 0.01% to about 3% by weight of a water-insoluble
solvent selected from the group consisting of:
(i) alkanes and alkenes having a flash point not lower than about
65.degree. C. (Tag closed cup), an initial boiling point not lower
than about 130.degree. C., a solidification point not above about
20.degree. C. and a carbon chain length from about 10 to about 18;
and
(ii) fatty acid esters of the formula ##STR7## in which R.sub.1 is
an alkyl group with from about 7 to about 17 carbon atoms and
R.sub.2 is an alkyl group with from 1 to about 10 carbon atoms, the
sum of carbon atoms in R.sub.1 and R.sub.2 being from about 8 to
about 23;
(b) from about 0.01% to about 0.5% by weight of a water-in-oil
emulsifier soluble in said water-insoluble solvent having an HLB
value of from about 2 to about 12 and consisting essentially of
from about 25% to 100% of emulsifier compounds with at least two
alkyl groups each having from about 9 carbon atoms to about 20
carbon atoms and selected from the group consisting of:
(i) dialkyl sulfosuccinic acid and alkali metal, alkaline earth
metal, ammonium, and mono-, di-, and tri-C.sub.1-4 alkyl and
alkanol ammonium salts of dialkyl sulfosuccinic acid, said alkyl
groups each containing from about 9 to about 20 carbon atoms;
(ii) quaternary ammonium compounds with more than one long chain
alkyl group selected from the group consisting of di-C.sub.9-20
alkyl ammonium chloride, bromide, methyl sulfate, nitrate and
acetate and di-C.sub.9-20 alkyl imadazolinium quaternary ammonium
compounds;
(iii) alkyl or alkyl ethoxy diesters of phosphoric acid having the
formula ##STR8## in which Both R.sub.1 and R.sub.2 are alkyl groups
containing from about 9 to about 20 carbon atoms, n and m are from
zero to about 8 and M is hydrogen or a salt forming cation, and
(iv) mixtures thereof; and
(c) from about 90% to about 99.6% water;
(2) allowing said fabrics to remain in contact with said washing
medium for at least 30 seconds; and
(3) adding or releasing to said aqueous medium containing said
fabric from about 0.01% to about 1% by weight of a water-soluble
surfactant having an HLB value of from about 11 to about 18,
selected from the group consisting of anionic, nonionic,
zwitterionic, amphoteric and cationic surfactants and mixtures
thereof.
10. The method of claim 9 wherein the concentration of said solvent
is from about 0.2% to about 1.2%, the concentration of said
water-in-oil emulsifier is from about 0.02% to about 0.2% and the
concentration of said water-soluble surfactant is from about 0.02%
to about 0.5%.
11. The method of claim 9 wherein the concentration of said solvent
is about 0.8% the concentration of said water-in-oil emulsifier is
about 0.1% and the concentration of said water-soluble surfactant
is from about 0.05% to about 0.15%.
12. The method of claim 9 which additionally consists essentially
of adding or releasing to said aqueous medium with said
water-soluble surfactant or any time thereafter from about 0.005%
to about 0.5% of a fabric sizing agent selected from the group
consisting of gelatinized starch and partially gelatinized starch
and from 0% to about 0.1% of a quaternary ammonium fabric softening
and anti-static agent selected from the group consisting of
(a) compounds having the formula ##STR9## wherein R.sub.1 is
hydrogen or an aliphatic group of from 1 to 22 carbon atoms;
R.sub.2 is an aliphatic group having from 12 to 22 carbon atoms;
R.sub.3 and R.sub.4 are each alkyl groups of from 1 to 3 carbon
atoms; and X is an anion selected from halogen, acetate, phosphate,
nitrate and methyl sulfate radicals;
(b) compounds having the formula ##STR10## wherein R.sub.6 is an
alkyl containing from 1 to 4, preferably from 1 to 2 carbon atoms,
R.sub.5 is an alkyl containing from 1 to 4 carbon atoms or a
hydrogen radical, R.sub.8 is an alkyl containing from 1 to 22,
preferably at least 15 carbon atoms, and X is an anion; and
(c) mixtures thereof.
13. The method of claim 9 wherein said solvent is an alkane with an
average of from about 10 to about 16 carbon atoms.
14. The method of claim 13 wherein said solvent stripping agent
comprise an anionic surfactant selected from the group consisting
of alkyl sulfates, alkyl benzene sulfonates, and alkyl polyoxyether
sulfates, said alkyl groups having from about 10 to about 20 carbon
atoms and said polyoxyether group having an average of from about 2
to about 4 moles of ethylene oxide.
Description
BACKGROUND OF THE INVENTION
Field of the Invention
This invention relates to compositions and methods for removing
oily soils from fabrics. More particularly, the invention relates
to the use of specific mixtures of water-insoluble solvents and
solvent soluble emulsifiers in aqueous washing media followed by
treatment with a composition incorporating a surface active agent
(surfactant) to remove residual solvent from the fabrics.
Current laundry products and procedures exhibit one or more
deficiencies when used to clean oil stains, particularly
hydrocarbon stains, from fabrics. Fatty triglyceride soils,
especially those arising from natural body secretions, present
another type of oily stain which is difficult to remove from modern
fabrics by means of simple aqueous laundering processes. Such
deficiencies are especially apparent when polyester or
polyester-cotton fabric blends soiled with various oily materials
are laundered in aqueous laundry baths.
Heretofore, effective oil removal from modern fabrics has largely
been accomplished by means of relatively inconvenient and expensive
methods involving non-aqueous dry cleaning processes. Another
approach for removal of oily stains has been pretreatment of soiled
areas of fabrics with liquid detergents or specific pretreatment
compositions prior to normal laundering. This approach has not
proven entirely satisfactory. It is not always practical to
identify the fabric areas which need special attention prior to
laundering. Results are often disappointing. Accordingly,
compositions and methods which would provide economical and
efficient removal of oily soils from fabrics employing conventional
household laundry equipment are desirable.
The present invention employs a sequential treatment of fabrics in
an aqueous washing medium with first, a water-insoluble solvent
containing about 3% to about 30% of a solvent soluble water-in-oil
emulsifier typically having an hydrophilic lipophilic balance (HLB)
value of from about 2 to about 12, and second, a composition
comprising a water soluble surfactant typically having an HLB value
of from about 11 to about 18.
State of the Art
Water-insoluble solvents containing surfactants have been
described. Typical utilities for such compositions are dry
cleaning, hard surface cleaning, and as bases for insecticide
compositions. U.S. Pat. Nos. 2,271,635; 2,326,772; 2,327,182; and
2,327,183 disclose dry cleaning solvents containing small amounts
of water or having the ability to emulsify small amounts of water
because of the content of surfactants. This aids in the removal of
water-soluble soils. Surfactants and emulsifiers disclosed
respectively in these patents are alkyl sulfates, alkyl benzene
sulfonates, and sulfonated aliphatic carboxylate-alcohol esters.
The disclosed surfactant levels are below 1% based on the weight of
solvent used in the dry cleaning process.
U.S. Pat. No. 3,101,239 (Warren et al) discloses Stoddard solvent
containing 1.5% to 3% of dioctyl sodium sulfosuccinate.
U.S. Pat. No. 3,277,013 (Gianladis) discloses waterless skin
cleaners containing mineral oil or deodorized kerosene and an
ethoxylated nonionic surfactant. The preferred surfactant level is
about 15% based on mineral oil or kerosene.
U.S. Pat. No. 3,352,790 (Sugarman) discloses dry cleaning solvents
containing 0.2 to 10% of a phosphate ester of an alkoxylated
nonionic.
U.S. Pat. No. 3,645,906 (Valenta et al) discloses water solvent
emulsions containing 15% to 30% of alkylated diphenyl oxide
sulfonates.
U.S. Pat. No. 3,707,506 (Lozo) discloses aqueous washing solutions
containing 0.01 to 5% of detergent compositions comprising 20 to
80% of a generally water-soluble monoalkyl nonionic surfactant and
80 to 20% kerosene.
U.S. Pat. No. 3,962,151 (Dekker) discloses kerosene containing
cationic emulsifiers and optionally nonionic detergents. The
utility is hard surface cleaning involving removal of the kerosene
and soil with a water flush.
While the use of various water-insoluble solvent and surfactant or
emulsifier mixtures is known, the detergent arts have not
heretofore recognized that certain combinations of solvents and
solvent soluble poly long chain alkyl emulsifiers provide
exceptional cleaning of fabrics with oily soils in an aqueous
medium, especially when the addition of this composition to the
aqueous medium is followed by the subsequent addition of a
composition comprising a water soluble surfactant with an HLB value
of from about 11 to about 18. It has now been discovered that
certain properly formulated mixtures of water-insoluble solvents
and solvent soluble water-in-oil emulsifiers typically with an HLB
value of from about 2 to about 12 are especially useful in aqueous
media for solubilizing oily soils and removing the same from
fabrics, particularly fabrics containing polyester fibers. In the
practice of this invention the addition of this oily soil
dissolving agent composition, comprising solvent and emulsifier, to
the aqueous washing medium is followed by the addition of a second
solvent stripping agent composition comprising a surfactant with an
HLB value of from about 11 to about 18. The combined treatment
provides cleaning of oily soils from fabrics comparable to that
obtained in a typical dry cleaning process. The compositions herein
are characterized by the speed with which they remove oily soils
from fabrics; hence they are useful for cleaning fabrics in the
relatively limited time available in the cleaning cycle of a home
laundering operation.
The oily soil solubilization step can be accomplished in as short a
time as 30 seconds even in cool water. Removal of retained solvent
by use of the solvent stripping agent also takes place rapidly,
easily with the fine fabric or wash wear cycle of automatic washing
machines.
It is an object of the present invention to provide compositions
and methods for removing oily soil from fabrics in a home laundry
operation.
A further object of this invention is to provide a prepackaged
cleaning product which contains the two cleaning compositions of
the invention in discrete units suitable for sequential addition to
an aqueous washing medium. A still further object herein is to
provide compositions which additionally comprise fabric care
ingredients for providing or restoring a desirable fabric
texture.
These and other objects are obtained herein, as will be seen by the
following disclosure.
SUMMARY OF THE INVENTION
The present invention encompasses a prepackaged cleaning product
for removing oily soil from fabrics in an aqueous washing medium
comprising:
(1) a discrete unit of an oily soil dissolving agent
comprising:
(a) from about 20% to about 97% of a water insoluble solvent
selected from the group consisting of:
(i) alkanes or alkenes having a flash point not lower than
65.degree. C. (Tag closed cup), an initial boiling point not lower
than about 130.degree. C., and a solidification point not above
about 20.degree. C.; and
(ii) fatty acid esters of the formula ##STR1## in which R.sub.1 is
an alkyl group with from about 7 to about 17 carbon atoms and
R.sub.2 is an alkyl group with from 1 to about 10 carbon atoms, the
sum of carbon atoms in R.sub.1 and R.sub.2 being from about 8 to
about 23; and
(b) from about 3% to about 30% by weight of a water-in-oil
emulsifier soluble in said solvent having an HLB value of from
about 2 to about 12 and comprising from about 25% to 100% of
emulsifier compounds with at least two alkyl groups each having at
least about 9 carbon atoms.
(2) a discrete unit of a solvent stripping agent comprising about
5% to 100% of a water soluble surfactant having an HLB value of
from about 11 to about 18, said discrete unit comprising from about
10% to about 80% by weight of the total cleaning product, said
discrete unit of solvent stripping agent being adapted for entry to
said aqueous washing medium at least about 30 seconds after entry
of said discrete unit of oily soil dissolving agent.
Preferably, the discrete units are the amount of oily soil
dissolving agent and solvent stripping agent suitable for a single
cleaning procedure. A preferred weight range for discrete units of
oily soil dissolving agent is from about 75 grams to about 1000
grams, more preferably from about 200 grams to about 800 grams. A
preferred weight range for discrete units of solvent stripping
agent is from about 50 grams to about 1000 grams, more preferably
from about 100 grams to about 500 grams. These weight ranges are
suitable for use in a typical upright automatic washing machine
with a water capacity of 10 to 15 gallons.
The oily soil dissolving agent is added to an aqueous washing
medium at a concentration of about 0.1% to about 3% by weight of
the aqueous washing medium. The solvent stripping agent is added to
provide a concentration from about 0.01% to about 1% by weight of a
water-soluble surfactant having an HLB value of from about 11 to
about 18 in the aqueous medium. The compositions herein may contain
additional ingredients to provide removal of other types of soils
or to provide fabric care properties so long as these ingredients
are compatible with the essential ingredients.
DETAILED DESCRIPTION OF THE INVENTION
The oily soil effective detergent compositions herein comprise
three essential ingredients; a solvent suitable for use in a
household washing machine, a water-in-oil emulsifier soluble in
said solvent, having an HLB value of from about 2 to about 12 and
at least about 25% by weight of emulsifier compounds having more
than one long chain hydrophobic group, and a water soluble
surfactant compounded separately from said solvent and said solvent
soluble emulsifier, said surfactant having an HLB value of from
about 11 to about 18. The water soluble surfactant is added or
otherwise released to the aqueous washing medium, or alternately to
an aqueous rinsing medium, at least about 30 seconds after addition
of the oily soil dissolving agent comprising a solvent and a
solvent soluble emulsifier.
Solvent
The choice of a solvent for the practice of this invention is based
on performance considerations, but limited by considerations of
safety and acceptability for use in home laundry equipment.
Flammability considerations require use of only those hydrocarbon
solvents that will not be easily flammable in either the undiluted
product form or as used in an aqueous washing medium. This excludes
"naphtha" and Stoddard Solvent with flash points below about
40.degree. C. to 50.degree. C. Halogenated solvents do not have any
substantial flammability problem but are undesirable for home use
because of odor and biological safety considerations. Although the
oily soil dissolving agent comprising the solvent and
solvent-soluble emulsifier is water insoluble, the oily soil
dissolving agent should be temporarily dispersible in the aqueous
washing medium so as to provide the opportunity of contact of the
solvent phase with all the fabric surface in the aqueous washing
medium. A composition containing a specified solvent and a suitable
solvent soluble emulsifier is substantive to fabrics, particularly
those of a hydrophobic nature such as polyester fabrics, and the
composition partially replaces adsorbed water on the fabrics.
Solvents which meet the criteria discussed above are: (1) alkanes
and alkenes having a flash point not lower than about 65.degree.
C., and specified boiling point and solidification point
characteristics, and (2) specified fatty acid esters.
The alkanes and alkenes suitable for use in the practice of the
invention have a flash point not lower than about 65.degree. C.,
preferably not lower than about 90.degree. C. (Tag closed cup
test), an initial boiling point not lower than about 130.degree.
C., and a solidification point not above about 20.degree. C. In
general, the preferred alkanes that meet these criteria will be
aliphatic hydrocarbons having the generic formula C.sub.n
H.sub.2n+2, in which n is from about 10 to about 18 (i.e., the
aliphatic series decane through octadecane). Although single
compounds are suitable for use in this invention, most commercially
available solvents that meet the boiling point and distillation
point criteria will be mixtures of aliphatic hydrocarbons. Examples
of suitable commercially available materials are Paraffin F
(Exxon), Isopar (Exxon), Varsol (Exxon), Norpar (Exxon), 95%
dodecane, and kerosene, especially deodorized kerosene.
Kerosene is a mixture of petroleum hydrocarbons comprising
principally alkanes having from 10 to 16 carbon atoms per molecule.
It constitutes the fifth fraction in the distillation of petroleum,
being collected after the petroleum ethers and before the oils.
Although kerosene is comprised mainly of alkanes, a typical
kerosene also includes alkyl derivatives of benzene and
naphthalene. Kerosene particularly suitable for use in this
invention is deodorized and decolorized by washing with sulfuric
acid followed by treatment with sodium plumbite solution and
sulfur.
The use of alkanes containing substantial molecular species with
carbon chain lengths over about 18 is undesirable because of a
tendency to distribute poorly in the aqueous washing medium. In
general, any alkane/alkene mixture should be freely pourable at
20.degree. C. In general, suitable alkanes will have a density at
20.degree. C. lower than about 0.8.
The fatty acid esters suitable as solvents for this invention are
described herein. Particularly suitable are the methyl, ethyl, and
propyl esters of fatty acids with a carbon chain length of from
about 8 to about 18.
The Solvent Soluble Emulsifier
The solvent soluble water-in-oil emulsifiers suitable for
incorporation in the solvents described above may be from any of
the usual classes of emulsifiers such as anionic, nonionic,
zwitterionic, amphoteric, and cationic.
The essential characteristics of this emulsifier are solubility in
the solvent employed, an HLB value of from about 2 to about 12 and
about a 25% to 100% content of emulsifier compounds with at least
two alkyl groups each having at least about 9 carbon atoms. In
general, these characteristics are not independent; a relatively
low HLB value is predictive of solubility in the solvents of this
invention and a poly-long chain alkyl structure tends to provide
both solvent solubility and low HLB values. Preferred emulsifiers
have a relatively low water solubility and consequently will tend
to partition preferentially to the solvent phase of a two phase
solvent-water system. As described more fully below, particularly
preferred emulsifiers with two or more long chain alkyl groups, are
dialkyl sulfosuccinic acid esters, salts of diesters of phosphoric
acid and quaternary ammonium salts with two or three long chain
alkyl groups.
The effectiveness of emulsifiers and surfactants as water-in-oil or
oil-in-water emulsifiers, wetting agents or solubilizing agents can
be predicted by the HLB value of the surfactant or emulsifier. This
relates to the principle that the emulsifying efficiency of a given
compound is associated with the polarity of the molecule. The
contribution of the polar hydrophilic head of the molecule and the
non-polar lipophilic tail is represented by a scale in which the
least hydrophilic material has low HLB numbers while high HLB
numbers correspond to increased water solubility. The HLB value of
surfactants or emulsifiers can be determined experimentally in a
well known fashion. The HLB value of compounds in which the
hydrophilic portion of the molecule is principally an alkylene
oxide, such as ethylene oxide, can be estimated by the weight ratio
of alkylene oxide portion to the lipophilic portion (e.g., a
hydrocarbyl radical). In general, surfactants or emulsifiers with
an HLB number below some value in the range of 10 through 12 will
be soluble or dispersible in the solvents of the present invention,
but poorly soluble in water. The critical HLB value for solvent
solubility varies somewhat with molecular structure. Surfactants
with an HLB number above about 11 will be water soluble or
dispersible and tend to be insoluble in solvents. Low HLB value
compounds promote the formation of water-in-oil emulsions while
high HLB value compounds promote the formation of oil-in-water
emulsions. In the practice of the present invention it is
undesirable initially to form highly stable oil-in-water emulsions
of the oily soil dissolving agent in the aqueous washing medium.
The composition is not sufficiently fabric substantive when
dispersed in water in the presence of surfactants with HLB values
above about 11 or 12.
Preferred solvent soluble anionic surfactants having an HLB value
of from about 2 to about 12 for the practice of the invention are
the salts of dialkyl esters of sulfosuccinic acids, wherein the
alkyl groups contain from about 9 to about 20 carbon atoms, and the
alkyl and alkyl polyethoxy diesters of phosphoric acid. Specific
examples of suitable sulfosuccinic acid esters are sodium
(bis)decyl sulfosuccinate and sodium (bis)tridecyl
sulfosuccinate.
Diesters of phosphoric acid useful in the practice of this
invention generally have the formula:
Although a preferred form of anionic emulsifier is a neutralized
salt (e.g., alkali metal, alkaline earth metal, ammonium, or mono-,
di-, and tri-C.sub.1-4 alkyl and alkanol ammonium salt), the
unneutralized acid form of anionic emulsifiers can be employed.
Mixtures of all of the above emulsifiers can be employed.
Preferred cationic surfactants for the practice of this invention
are quaternary ammonium compounds with more than one long chain
alkyl (e.g. C.sub.9-20) group such as ditallowdimethyl ammonium
chloride, bromide, methyl sulfate, nitrate, acetate, etc., and
dialkyl imidazolinium quaternary ammonium compounds such as
methyl-1-stearylamido-ethyl-2-stearlamidoimidazolinium methyl
sulfate, chloride, bromide, nitrate, acetate, etc.
Water Soluble Surfactant
The water soluble relatively high HLB surfactant used in the
practice of this invention is characterized by water solubility and
an HLB value of from about 11 to about 18. Water soluble
surfactants in this HLB range generally have the ability to form
stable oil-in-water emulsions or even clear dispersions of oil or
solvents in water. As discussed above the initial presence of water
soluble surfactants with HLB values above about 11 adversely
affects the substantivity of the solvent to fabrics in the aqueous
washing medium. Adsorption of the oily soil dissolving agent
comprising solvent and the solvent soluble emulsifier proceeds
rapidly, however, and the water soluble surfactant may enter or be
added to the aqueous washing medium at any interval of at least
about 30 seconds after addition of the oily soil solvent
composition. A delay of from about 2 to about 5 minutes is optimum
from the standpoints of performance and convenience. Any method of
obtaining this delay is acceptable. In one embodiment of this
invention, the oily soil dissolving agent and the solvent stripping
agent are separately compounded and packaged. In another embodiment
of this invention the solvent stripping agent comprising a water
soluble surfactant is compounded with the oily soil dissolving
agent, but is restrained from mixing with the oily soil dissolving
agent and restrained from immediate release into the aqueous
washing medium by a coating, or matrix, of solvent insoluble
material. Desirably, such coating or matrix shall also have the
ability to delay effective addition of the solvent stripping agent
to the aqueous washing medium until at least about 30 seconds after
the total composition is added to the aqueous washing medium
containing the fabrics to be cleaned.
The water soluble surfactant of this invention having an HLB value
of from about 11 to about 18 may be selected from the usual classes
of surfactants, namely, anionics, nonionics, zwitterionics,
amphoteric, and cationic surfactants. Suitable surfactants may be a
mixture of various classes of detergents although the combination
of anionic and cationic surfactants may present compatibility
problems. The water soluble surfactants can be selected from the
surfactants disclosed hereinafter and mixtures thereof, so long as
the HLB limits are observed for the total water soluble surfactant
system.
Water soluble high HLB anionic surfactants suitable for use in the
practice of this invention include alkali metal soaps and the
alkali metal, alkaline earth metal, ammonium, and substituted
ammonium salts of organic sulfuric reaction products. Examples of
salts of organic sulfuric reaction products are sodium alkyl
sulfate and sodium alkyl benzene sulfonate wherein the alkyl group
contains from about 10 to about 20 carbon atoms. Other preferred
surfactants of this class are paraffin sulfonates and olefin
sulfonates in which the alkyl or alkenyl group contains from about
10 to about 20 carbon atoms.
Other preferred water soluble anionic surfactants useful herein are
alkyl ether sulfates having the formula RO(C.sub.2 H.sub.4 O).sub.x
SO.sub.3 M wherein R is alkyl or alkenyl of about 10 to about 20
carbon atoms, x is 1 to 30, and M is a water-soluble cation. The
alkyl ether sulfates useful in the present invention are
condensation products of ethylene oxide and monohydric alcohols
having about 10 to about 20 carbon atoms. Preferably, R has 12 to
18 carbon atoms. The alcohols can be derived from natural fats,
e.g., coconut oil or tallow, or can be synthetic. Such alcohols are
reacted with 1 to 30, and especially 3, molar proportions of
ethylene oxide and the resulting mixture of molecular species is
sulfated and neutralized.
Specific examples of alkyl ether sulfates of the present invention
are sodium coconut alkyl triethylene glycol ether sulfate, lithium
tallow alkyl triethylene glycol ether sulfate, and sodium tallow
alkyl hexaoxyethylene sulfate. Preferred alkyl ether sulfates are
those comprising a mixture of individual compounds, said mixture
having an average alkyl chain length of from about 12 to 16 carbon
atoms and an average degree of ethoxylation of from about 1 to 4
moles of ethylene oxide.
Additional examples of anionic surfactants useful herein are the
compounds which contain two anionic functional groups. These are
referred to as di-anionic surfactants. Suitable dianionic
surfactants are the disulfonates, disulfates, or mixtures thereof
which may be represented by the following formula:
where R is an acyclic aliphatic hydrocarbyl group having 15 to 20
carbon atoms and M is a water-solubilizing cation, for example, the
C.sub.15 to C.sub.20 disodium 1,2-alkyldisulfates, C.sub.15 to
C.sub.20 dipotassium-1,2-alkyldisulfonates or disulfates, disodium
1,9-hexadecyl disulfates, C.sub.15 to C.sub.20 disodium
1,2-alkyldisulfonates, disodium 1,9-stearyldisulfates and
6,10-octadecyldisulfates.
Water soluble nonionic surfactants having an HLB value of from
about 11 to about 18 and useful herein include:
1. The polyethylene oxide condensates of alkyl phenols. These
compounds include the condensation products of alkyl phenols having
an alkyl group containing from about 6 to 12 carbon atoms in either
a straight chain or branched chain configuration, with ethylene
oxide, the said ethylene oxide being present in amounts equal to 5
to 25 moles of ethylene oxide per mole of alkyl phenol. The alkyl
substituent in such compounds may be derived, for example, from
polymerized propylene or isobutylene, octene or nonene. Examples of
compounds of this type include nonyl phenol condensed with about
9.5 moles of ethylene oxide per mole of nonyl phenol and dodecyl
phenol condensed with about 12 moles of ethylene oxide per mole of
dodecyl phenol. Commercially available nonionic surfactants of this
type include Igepal CO-610 marketed by the GAF Corporation, and
Triton X-45, X-114, X-100 and X-102, all marketed by the Rohm and
Haas Company.
2. The condensation products of aliphatic alcohols with ethylene
oxide. The alkyl chain of the aliphatic alcohol may either by
straight or branched and generally contains from about 8 to about
22 carbon atoms. Examples of such ethoxylated alcohols include the
condensation product of about 6 moles of ethylene oxide with 1 mole
of tridecanol, myristyl alcohol condensed with about 10 moles of
ethylene oxide per mole of myristyl alcohol, the condensation
product of ethylene oxide with coconut fatty alcohol wherein the
coconut alcohol is a mixture of fatty alcohols with alkyl chains
varying from 10 to 14 carbon atoms and wherein the condensate
contains about 6 moles of ethylene oxide per mole of alcohol, and
the condensation product of about 9 moles of ethylene oxide with
the above-described coconut alcohol. Examples of commercially
available nonionic surfactants of this type include Tergitol 15-S-9
marketed by the Union Carbide Corporation, Neodol 23-6.5 marketed
by the Shell Chemical Company.
3. The condensation products of ethylene oxide with a hydrophobic
base formed by the condensation of propylene oxide with propylene
glycol. The hydrophobic portion of these compounds has a molecular
weight of from about 1500 to 1800 and exhibits water insolubility.
The addition of at least about 30% by weight of polyoxyethylene
moieties to this hydrophobic portion provides water-solubility to
the molecule. Examples of compounds of this type include certain of
the commercially available Pluronic surfactants marketed by the
Wyandotte Chemicals Corporation.
4. The condensation products of ethylene oxide with the product
resulting from the reaction of propylene oxide and ethylenediamine.
The hydrophobic base of these products consists of the reaction
product of ethylenediamine and excess propylene oxide, said base
having a molecular weight of from about 2500 to about 3000. This
base is condensed with ethylene oxide to the extent that the
condensation product contains from about 40 to about 80% by weight
of polyoxyethylene and has a molecular weight of from about 5,000
to about 11,000. Examples of this type of nonionic surfactant
include certain of the commercially available Tetronic compounds
marketed by the Wyandotte Chemicals Corporation.
5. Surfactants having the formula R.sup.1 R.sup.2 R.sup.3
N.fwdarw.O (amine oxide surfactants) wherein R.sup.1 is an alkyl
group containing from about 10 to about 18 carbon atoms, from 0 to
about 2 hydroxy groups and from 0 to about 5 ether linkages, there
being at least one moiety of R.sup.1 which is an alkyl group
containing from about 10 to about 18 carbon atoms and no ether
linkages, and each R.sup.2 and R.sup.3 is selected from the group
consisting of alkyl groups and hydroxyalkyl groups containing from
1 to about 3 carbon atoms. Specific examples of amine oxide
surfactants include: dimethyldodecylamine oxide,
dimethyltetradecylamine oxide, ethylmethyltetradecylamine oxide,
cetyldimethylamine oxide, dimethylstearylamine oxide,
cetylethylpropylamine oxide, diethyldodecylamine oxide,
diethyltetradecylamine oxide, dipropyldodecylamine oxide
bis-(2-hydroxyethyl)dodecylamine oxide,
bis(2-hydroxyethyl)-3-dodecoxy-2-hydroxypropylamine oxide,
(2-hydroxypropyl)methyltetradecylamine oxide, dimethyloleylamine
oxide, dimethyl-(2-hydroxydodecyl)amine oxide, and the
corresponding decyl, hexadecyl and octadecyl homologs of the above
compounds.
Ampholytic synthetic detergents can be broadly described as
derivatives of aliphatic, or alkyl substituted hetero cyclic,
secondary and tertiary amines in which the aliphatic radical may be
straight chain or branched and wherein one of the aliphatic
substituents contains from about 8 to 18 carbon atoms and at least
one contains an anionic water-solubilizing group, e.g., carboxy,
sulfonate, sulfate. Examples of compounds falling within this
definition are sodium 3-(dodecylamino)propionate, sodium
2-(dodecylamino)ethyl sulfate, sodium
2-(dimethylamino)octadecanoate, disodium
3-(N-carboxymethyldodecylamino)propane-1-sulfonate, disodium
octadecyl-iminodiacetate, sodium
1-carboxymethyl-2-undecylimidazole, and sodium
N,N-bis(2-hydroxyethyl)-2-sulfato-3-dodecoxy-propylamine. Sodium
3-(dodecylamino)propane-1-sulfonate is preferred.
Zwitterionic surfactants can be broadly described as derivatives of
secondary and tertiary amines, derivatives of heterocyclic
secondary and tertiary amines, or derivatives of quaternary
ammonium, quaternary phosphonium or tertiary sulfonium compounds.
The cationic atom in the quaternary compound can be part of a
heterocyclic ring. In all of these compounds there is at least one
aliphatic group, straight chain or branched, containing from about
3 to 18 carbon atoms and at least one aliphatic substituent
attached to an "onium" atom and containing an anionic
water-solubilizing group, e.g., carboxy, sulfonate, sulfate,
phosphate, or phosphonate. Examples of zwitterionic surfactants
include 3-(N,N-dimethyl-N-hexadecylammonio)-propane-1-sulfonate;
3-(N,N-dimethyl-N-hexadecylammonio)-2-hydroxypropane-1-sulfonate;
N,N-dimethyl-N-dodecylammonio acetate;
3-(N,N-dimethyl-N-dodecylammonio)propionate;
2-(N,N-dimethyl-N-octadecylammonio)ethyl sulfate;
3-(P,P-dimethyl-P-dodecylphosphonio)propane-1-sulfonate;
2-(S-methyl-S-tert-hexadecylsulfo)ethane-1-sulfonate;
3-(S-methyl-S-dodecylsulfonio)propionate;
N,N-bis(oleylamidopropyl-N-methyl-N-carboxymethylammonium betaine;
N,N-bis(stearamidopropyl)-N-methyl-N-carboxymethylammonium betaine;
N-(stearamidopropyl)-N-dimethyl-N-carboxymethylammonium betaine;
3-(N-4-n-dodecylbenzyl-N,N-dimethylammonio)propane-1-sulfonate; and
3-(N-dodecylphenyl-N,N-dimethylammonio)-propane-10- sulfonate.
Cationic surfactants having water solubility and an HLB value of
from about 11 to about 18, are useful in the practice of this
invention. Particularly useful are cationic surfactants in mixtures
with nonionic surfactants as disclosed in copending commonly
assigned U.S. Ser. Nos. 811,219; 811,220 and 811,221 all filed June
29, 1977.
Examples of useful water soluble cationic surfactants are
trimethyldodecyl ammonium chloride and the condensation product of
a primary fatty amine having a chain length of 12 to 18 carbon
atoms with 5 to 15 moles of ethylene oxide.
Adjuvant Materials
The oily soil dissolving agent comprising a solvent and solvent
soluble emulsifier and the solvent stripping agent comprising a
water soluble surfactant need not contain other ingredients for
effective oily soil removal from fabrics. Either composition may,
however, optionally contain other materials, for example, from 0%
to about 77% in the oily soil dissolving agent and from 0% to about
95% in the solvent stripping agent. Detergency builders are useful
adjuvants. Such builders can be employed in the oily soil
dissolving agent at concentrations of from 0% to about 77% by
weight and in the solvent stripping agent at concentrations of from
0% to about 95% by weight. Useful builders herein include any of
the conventional inorganic and organic builder salts.
Such detergency builders can be, for example, water soluble salts
of phosphates, pyrophosphates, orthophosphates, polyphosphates,
phosphonates, carbonates, polyhydroxysulfonates, silicates,
polyacetates, carboxylates, polycarboxylates and succinates.
Specific examples of inorganic phosphate builders include sodium
and potassium tripolyphosphates, pyrophosphates, and
hexametaphosphates. The polyphosphonates specifically include, for
example, the sodium and potassium salts of ethylene diphosphonic
acid, the sodium and potassium salts of ethane
1-hydroxy-1,1-diphosphonic acid and the sodium and potassium salts
of ethane-1,1,2-triphosphonic acid. Examples of these and other
phosphorous builder compounds are disclosed in U.S. Pat. Nos.
3,159,581; 3,213,030; 3,422,021; 3,422,137; 3,400,176 and
3,400,148, incorporated herein by reference.
Non-phosphorus containing sequestrants can also be selected for use
herein as detergency builders.
Specific examples of non-phosphorus, inorganic builder ingredients
include water-soluble inorganic carbonate, bicarbonate, and
silicate salts.
Water-soluble, organic builders are also useful herein. For
example, the alkali metal, ammonium and substituted ammonium
polyacetates, carboxylates, polycarboxylates and
polyhydroxysulfonates are useful builders in the present
compositions and processes. Specific examples of the polyacetate
and polycarboxylate builder salts include sodium, potassium,
lithium, ammonium and substituted ammonium salts of ethylene
diamine tetraacetic acid, nitrilotriacetic acid, oxydisuccinic
acid, mellitic acid, benzene polycarboxylic acids, and citric
acid.
Preferred non-phosphorous builder materials herein include sodium
carbonate, sodium bicarbonate, sodium silicate, sodium citrate,
sodium oxydisuccinate, sodium mellitate, sodium nitrilotriacetate,
and sodium ethylenediaminetetraacetate, and mixtures thereof.
Other preferred builders herein are the polycarboxylate builders
set forth in U.S. Pat. No. 3,308,067, Diehl, incorporated herein by
reference. Examples of such materials include the water-soluble
salts of homo- and co-polymers of aliphatic carboxylic acids such
as maleic acid, itaconic acid, mesaconic acid, fumaric acid,
aconitic acid, citraconic acid and methylenemalonic acid.
Additionally, preferred builders herein include the water-soluble
salts, especially the sodium and potassium salts, of
carboxymethyloxymalonate, carboxymethyloxysuccinate,
cis-cyclohexanehexacarboxylate, cis-cyclopentanetetracarboxylate
and phloroglucinol trisulfonate.
A further class of detergent builders are certain insoluble
aluminosilicates. Detergent compositions incorporating these
aluminosilicate materials are disclosed in Belgian Patent No.
814,874 issued Nov. 12, 1974, the disclosures of which are herein
incorporated by reference.
The compositions herein can also optionally contain all manner of
additional materials commonly found in laundering and cleaning
compositions including diluents such as water and inert inorganic
salts. Thickeners and soil suspending agents such as
carboxymethyl-cellulose and the like can be included in the
compositions. Enzymes, especially the thermally stable proteolytic
and lipolytic enzymes commonly used in high temperature laundry
detergent compositions, can also be present herein. Various
perfumes, optical bleaches and the like can be present to provide
the usual benefits occasioned by the use of such materials in
detergent compositions. Oxygen bleaches can also be present as a
component of the compositions herein. It is to be recognized that
the addition of all such adjuvant materials is practical, inasmuch
as they are compatible and stable in the compositions herein.
The solvent stripping agent may additionally comprise adjuvants
useful in the context of the care or treatment of fabrics.
In a preferred embodiment the solvent stripping agent comprises
from about 0.5% to about 15% of a fabric sizing agent such as
gelatinized or partially gelatinized starch. Particularly preferred
are gelatinized or partially gelatinized natural starches such as
partially gelatinized corn starch. Additional examples of sizing
agents and starches suitable for use in the practice of the present
invention are those materials disclosed in U.S. Pat. No. 2,702,755
issued to Chaney Feb. 22, 1955; U.S. Pat. No. 2,999,031 issued to
Katzback Sept. 5, 1961; and U.S. Pat. No. 3,332,795 issued to Black
et al July 25, 1967, the disclosures of which are incorporated
herein by reference. This provides or restores a body to the
treated fabrics that is associated with new fabrics or garments. In
an especially preferred embodiment the solvent stripping agent
comprises a fabric conditioning agent selected from fabric
softening agents and antistatic agents. Quaternary ammonium
compounds such as ditallow dimethyl ammonium chloride and certain
imidazolinium compounds, e.g.,
methyl-1-stearylamidoethyl-2-stearylamidoimidazolinium methyl
sulfate, provide both fabric softening and an antistatic benefit.
Other fabric softening and antistatic agents suitable for
incorporation in the solvent stripping agent are disclosed in U.S.
Pat. No. 4,018,688 issued to Pracht et al Apr. 19, 1977
incorporated herein by reference. It should be recognized that
compatibility considerations can limit the incorporation of
cationic softeners and cationic anti-static agents into solvent
stripping agents comprising anionic surfactants. A preferred level
of a quaternary ammonium compound in the solvent stripping agent is
from about 0.1% to about 3%. The use of a fabric softening agent in
combination with a fabric sizing agent is particularly desirable.
The resulting fabric texture can be described as having "body"
without stiffness.
Other adjuvants useful in the solvent stripping agent composition
are soil release polymers such as ethylene oxide terphthalate
co-polymers and hydroxybutyl cellulose. Soil release agents are
usefully present at concentrations up to 50% by weight of solvent
stripping agent or at a concentration of from about 0.01% to about
1%, preferably about 0.1%, by weight of the aqueous washing
medium.
In the method and aqueous washing medium composition aspect of the
present invention the solvent selected from alkanes, alkenes and
fatty acid esters as defined above should be present at a
concentration by weight of from about 0.1% to about 3% in the
aqueous washing medium. A concentration range of from about 0.2% to
about 1.2% is preferred and a concentration of about 0.8% is most
preferred. The solvent soluble emulsifier should be present in a
concentration of from about 0.01% to about 0.5%, preferably from
about 0.02% to about 0.2% and most preferably about 0.1%. The water
soluble surfactant component of the solvent stripping agent should
be subsequently added or released to provide a concentration of
from about 0.01% to about 1% in the aqueous washing medium;
preferably the concentration of this surfactant is from about 0.02%
to about 0.5%, and most preferably from about 0.05% to about
0.15%.
When utilized, a fabric sizing agent can be added or released to
the aqueous washing medium at a concentration of from about 0.005%
to about 0.5% by weight, a quaternary ammonium fabric softening and
antistatic agent can be added or released to the aqueous washing
medium at a concentration of from 0% to about 0.1% by weight, and a
soil release agent such as an ethylene oxide terephthalate
copolymer or hydroxybutyl cellulose can be added at a concentration
of from 0% to about 1% by weight. Preferably these fabric care
materials are added with the water-soluble surfactant or at any
time thereafter. Addition of fabric care ingredients can be in a
separate aqueous medium such as a rinse.
EXAMPLE I
Swatches of polyester knit and polyester/cotton blend fabrics were
artificially soiled with oily soils consisting of dirty motor oil,
mineral oil, bacon grease, margarine, liquid vegetable oil, and
suntan oil. These soiled swatches were then washed in a
conventional washing machine using the wash-wear/permanent press
cycle in 100.degree. F. water of 7 grains/gallon hardness (as
CaCO.sub.3), and were dried and graded visually by a panel of
judges for an estimate of the percent removal of the stain relative
to stained but unwashed swatches. Average percent removal grades
are given below for formulations of the cleaning system herein
described. All formulations provided a 0.8% concentration of alkane
and a 0.1% of sulfosuccinic diester emulsifier in the aqueous wash
medium.
______________________________________ Oily Soil Dissolving Agent
Average % Removal Ingredients of All Soils
______________________________________ C.sub.12 --C.sub.14 paraffin
blend bis-tridecyl ester of sodium sulfosuccinate (invention) 99+%
C.sub.12 paraffin dihexyl ester of sodium sulfosuccinate
(comparison) 78% C.sub.12 --C.sub.14 paraffin blend dioctyl ester
of sodium sulfosuccinate (comparison) 63% C.sub.12 paraffin dioctyl
ester of sodium sulfosuccinate (comparison) 60% Range of cleaning
of typical laundry detergent product (comparison) 50-60% Typical
cleaning of solvent dry cleaning process with pre-spotting of
stains (comparison) 100% ______________________________________
The above evaluation indicated that the bis-tridecyl ester of
sodium sulfosuccinate in a C.sub.12-14 alkane delivers oily soil
cleaning in an aqueous wash equivalent to dry cleaning. The more
water-soluble (higher HLB) structures of the other emulsifiers
provided substantially less satisfactory results.
The fabrics cleaned with the compositions above were not stripped
of residual oily soil dissolving agent.
EXAMPLE II
The equilibrium distribution ratio of emulsifiers between an oil
phase and a water phase is a useful indicator of their relative
HLB's and suitability for use in the present invention. Since the
method for experimental determination of an HLB value is tedious
and relatively insensitive, emulsifiers for possible use in the
practice of the present invention were evaluated for distribution
of 2 parts of emulsifer between 18 parts of dodecane and 80 parts
of water. The emulsifier was initially dissolved in the dodecane.
The two phase system was then shaken to equilibrium and the
separated layers were analyzed. Results are given for room
temperature equilibrium. Values below were generated for
emulsifiers used in Example 1:
______________________________________ Percent of Emulsifier
Ingredient in Oil Phase ______________________________________
Dioctyl sulfosuccinate, sodium salt 9% (bis) tridecyl
sulfosuccinate, sodium salt 100%
______________________________________
EXAMPLE III
Formula ingredients were screened for cleaning effectiveness in a
reduced scale simulated washing machine about two liters in volume.
Polyester/cotton blend swatches were soiled, cleaned at 70.degree.
F. in the aqueous washing media detailed below, and graded as in
Example I. Percent cleaning grades of approximately 90% or higher
in this test were considered "clean". Redeposition of the dark
components of the oily soils along with the residual oily soil
dissolving agent resulted in a darkening of otherwise clean
polyester tracer swatches in the bath as shown by the depression of
a mechanically read whiteness grade.
______________________________________ Percent Tracer Ingredients
Soil Removal Whiteness ______________________________________ 0.8%
petroleum paraffin, (C.sub.12 --C.sub.14) plus: (1) 0.1% (bis)
tridecyl sodium sulfosuccinate (invention) 93% 80 (2) 0.1% dihexyl
sodium sulfo- succinate (comparison) 76% 81 (3) 0.1% dicoco
dimethyl ammonium chloride (invention) 89% 75 (4) 0.1% coco
trimethyl ammonium chloride (comparison) 53% 81 (5) 0.1% complex
organic phosphate diester, sodium salt (invention) 91% -- (6) 0.1%
polyethoxylated linear 47% -- alcohol, C.sub.17 H.sub.35 O (C.sub.2
H.sub.4 O).sub.2 H (comparison 100.degree. F.) (7) No emulsifier
added to dodecane (comparison) 83% 48
______________________________________
The results above provide three examples of emulsifier/solvent
systems of the present invention. The relatively higher water
solubility of the emulsifiers in Compositions Nos. 2 and 4 place
them outside the desired performance range. The polyethoxylated
alcohol (Composition No. 6) has a calculated HLB value of about 5,
but does not possess the polyalkyl structure necessary for practice
of the present invention.
Cleaning of the dodecane alone is shown, but the gross solvent
phase deposition demonstrated by the low whiteness grade of the
tracer is indicative of the need for an emulsifier to at least
partially disperse the solvent phase in the wash. The cleaning
grade here is deceptively high; the oily stains were largely
obscured by the solvent deposition rather than being removed.
EXAMPLE IV
Small scale cleaning tests were performed to determine the effect
of a stripping step on residual oily soil dissolving agent on
fabrics. The procedure of Example III was generally followed,
except that the oily soil dissolving agent was dyed with an
oil-soluble red dye. The agent residual on rinsed and dried tracer
fabrics was measured by the shift toward red intensity of
reflectance values on a Hunter Color Difference Meter.
__________________________________________________________________________
Shift in Hunter "a" value of washed vs. Ingredients (wash conc.)
unwashed polyester tracer
__________________________________________________________________________
(1) 0.8% Paraffin "F" (Exxon) (C.sub.12-14 petroleum paraffin) 0.1%
Emcol 4600 (active basis) by Witco [(bis) tridecyl sulfosuccinate
sodium salt] +9.0 (2) Ingredients of NO. 1, plus: 0.13% Neodol
23-6.5 by Shell (ethoxylated C.sub.12-13 alcohols) added 2 minutes
after cleaning system +3.4 (3) Ingredients of NO. 1, plus: 0.13% Mg
(LAS).sub.2 (magnesium-neutralized C.sub.11.4 alkylbenzene
sulfonate), added 2 minutes after cleaning system +2.8 (4) 0.8%
Paraffin "F" 0.1% Emphos PS-21A by Witco (complex organic phosphate
ester, acid) +6.8 (5) Ingredients of No. 4, plus: 0.13% Neodol
23-6.5 added 2 minutes after cleaning system +3.6
__________________________________________________________________________
The reduction of the residual solvent shown above was readily
apparent by feel, smell, and appearance of the fabrics.
The importance of the delay of stripper was shown in a full scale
washing machine cycle test wherein Composition No. 3 above was
tested with the two minute delay and with the solvent stripping
agent Mg(LAS).sub.2 added to the water simultaneously with the
other ingredients;
______________________________________ Percent removal Stripper
Surfactant: of oily soil stains
______________________________________ Added simultaneously 72%
Added after two minutes delay 94%
______________________________________
As is apparent from these results, the immediate addition of a type
of surfactant determined to be an effective solvent stripping agent
causes interference with the cleaning process by stabilizing an
oil-in-water emulsion too early in the cycle.
EXAMPLE V
Compositions formulated as follows are produced.
______________________________________ Oily Soil Dissolving Agent
Paraffin F (Exxon) 84.7% Sodium (bis) tridecyl sulfosuccinate 10.5%
Ethanol 2.0% Water, perfume, & misc. Remainder Solvent
Stripping Agent Sodium C.sub.12 alkyl benzene sulfonate 16%
Gelatinized cornstarch 3% Preservative and perfume 0.24 Water and
miscellaneous Remainder ______________________________________
The above compositions are tested for their cleaning performance on
a variety of stains. The contents of a bottle containing 500
milliliters of the oily soil dissolving agent are added to a
washing machine containing 12 gallons of water at 40.degree. C. and
5 garments intentionally soiled with oily soils, (dirty motor oil,
mineral oil, suntan oil, liquid vegetable oil, bacon grease, and
margarine).
Three minutes after the start of agitation and addition of the oily
soil solvent, the contents of a bottle containing 350 milliliters
of the solvent stripping agent are added to wash water. Agitation
is continued for a total of 10 minutes and the programmed washing
machine cycle of extraction, deep rinse, and spin dry extraction is
completed.
All oily soils on the test garments are effectively removed.
Residual stains are clearly evident on duplicate garments soiled in
the same manner but washed with a conventional granular laundry
detergent.
Ditallowdimethyl ammonium chloride, dicocodimethyl ammonium
chloride methyl-1-stearylamido-ethyl-2-stearylamido imidazolinium
methyl sulfate, and the diester of phosphoric acid and a
C.sub.12-15 alcohol (sodium salt) are substituted on an equal
weight basis for sodium(bis) tridecyl sulfosuccinate and
substantially equivalent results are obtained.
EXAMPLE VI
The following compositions were produced and the evaluations are
representative of the compositions of the present invention.
Results were consistent with the excellent cleaning of oily soils
and the low fabric residual solvent levels provided by the practice
of the invention.
The solvent stripping agent in this evaluation was encapsulated in
pharmaceutical gelatin capsules, size 000, with each capsule
containing 1.24 g. of solvent stripping agent. The gelatin capsules
were dropped into the bottle of oily soil dissolving agent and were
observed to be unaffected by it. When this entire bottle was
emptied into the wash water the capsules were observed to dissolve,
and ruptured approximately 1 to 2 minutes after addition. Both
effective cleaning and solvent removal were achieved on
fabrics.
Oily Soil Dissolving Agent System Ingredients (wash conc.)
0.8% Paraffin "F"
0.1% Emcol 4600, dry basis (Witco Chemical Corp. trademark for
(bis) tridecyl sulfosuccinate)
Stripping System Ingredient (wash conc.)
0.13% Neodol 23-6.5 (Shell Chemical Co. trademark for C.sub.12-13
alcohol ethoxylated with an average of 6.5 moles of ethylene oxide
per mole of alcohol) encapsulated in gelatin and immersed in the
Oily Soil Dissolving Agent
B
The solvent stripping agent composition in this evaluation was
processed into a dry granulated product and added to the wash at
essentially the same time as the liquid oily soil dissolving agent.
The slower kinetics of dissolution of the granule into the aqueous
washing medium delayed effective entry of the stripping agent
surfactant sufficiently to give overall results approximating a
delayed addition of the surfactant.
Oily Soil Dissolving System Ingredients (wash conc.)
0.8% Paraffin "F"
0.1% Emcol 4600, dry basis
Solvent Stripping Agent System Ingredients (wash conc.)
0.325% of a granular product containing:
20% Mg(LAS).sub.2
40% Na.sub.2 SO.sub.4
30% MgSO.sub.4
3% Na.sub.2 CO.sub.3
7% Water
The solvent stripping agent in Example B is replaced by the
following granular compositions:
1.
20% sodium C.sub.12 LAS (linear alkyl benzene sulfonate)
20% sodium sulfate
50% sodium tripolyphosphate
10% water
2.
6% sodium C.sub.18 alkyl sulfate
6% sodium C.sub.13 linear alkyl benzene sulfonate
6% sodium C.sub.14-16 alkyl triethoxy sulfate
12% sodium silicate
30% sodium sulfate
30% sodium carbonate
10% water
Substantially similar results are obtained.
A further delay in delivery of the solvent stripping agent to the
aqueous washing medium in Example B is achieved by enclosing the
granular product in a packet of water-soluble film. Examples of
suitable film materials are polyvinyl alcohol and gelatin.
EXAMPLE VII
The Paraffin "F" of Example VI is replaced with isopropyl
myristate, with the methyl ester of coconut fatty acid, and with
kerosene. Substantially the same effective cleaning and solvent
removal are obtained.
EXAMPLE VIII
The concentration of Paraffin "F" in Example VI is reduced to 0.4%
in the aqueous washing medium and the concentration of Emcol 4600
is reduced to 0.05%. When used with a solvent stripping agent
providing 0.1% of sodium C.sub.12 alkyl benzene sulfonate effective
cleaning and solvent removal are obtained.
EXAMPLE IX
Compositions formulated as follows are produced.
______________________________________ Oily Soil Dissolving Agent
Paraffin F (Exxon) 89% Ditallowdimethyl ammonium chloride 8%
Isopropyl Alcohol 2% Solvent Stripping Agent C.sub.9-11 (EO) 8 -
i.e. 30% C.sub.9-11 alcohol condensed with an average of 8 moles of
ethylene oxide Gelatinized cornstarch 2% Ditallowdimethyl ammonium
chloride 0.5% Ethylene oxide terephthalate copolymer 5% Water &
misc. remainder ______________________________________
The above compositions are tested for their cleaning performance on
a variety of stains. The contents of a bottle containing 500
milliliters of the oily soil dissolving agent are added to a
washing machine containing 12 gallons of water at 40.degree. C. and
5 garments intentionally soiled with oily soils, (dirty motor oil,
mineral oil, suntan oil, liquid vegetable oil, bacon grease, and
margarine).
Three minutes after the start of agitation and addition of the oily
soil solvent, the contents of a bottle containing 350 milliliters
of the solvent stripping agent are added to wash water. Agitation
is continued for a total of 10 minutes and the programmed washing
machine cycle of extraction, deep rinse, and spin dry extraction is
completed. All oily soils on the test garments are effectively
removed. Residual stains are clearly evident on duplicate garments
soiled in the same manner but washed with a conventional granular
laundry detergent.
The solvent stripping agent is replaced by the following
composition:
______________________________________ C.sub.9-11 (EO).sub.8 33%
Triethanolamine 11% C.sub.11-12 linear alkyl benzene 11% sulfonic
acid Oleic acid 1% Ethanol 5% Potassium hydroxide 1.8% Citric acid
0.1% Water & Misc. Balance
______________________________________
Substantially the same cleaning results are obtained. Fabric
texture and "body" subjectively graded is considered somewhat less
desirable.
* * * * *